1-heterocyclyl methyl-2-nitro-or-cyanoiminidazoline salts, process for their preparation, pesticidal composition containing them, and pesticidal method of using them

ABSTRACT

The present invention relates to salts of imidazoline derivatives of the formula I ##STR1## in which R represents hydrogen or alkyl, 
     Y represents nitro or cyano, 
     W represents an optionally substituted 5- or 6-membered heterocyclic radical and 
     Z represents one equivalent of an alkali metal or alkaline earth metal or of an [NR 1  R 2  R 3  R 4  ] grouping, wherein 
     R 1 , R 2 , R 3  and R 4  are identical or different and represent hydrogen, alkyl, optionally substituted cycloalkyl or optionally substituted benzyl, 
     and to their preparation and their use as agents for controlling pests.

This application is a 371 of PCT/EP97/00475, which was filed on Feb. 3,1997.

The present invention relates to novel salts of imidazoline derivatives,a process for their preparation and their use for controlling animalpests.

It is already known that certain alkylated imidazoline derivatives, suchas, for example,1-(2-chloropyrimidin-5-yl)-3-methyl-2-nitroiminoimidazoline, haveinsecticidal properties (cf., for example, EP-A 0 315 826). However, theactivity and range of action of these compounds is not always completelysatisfactory, especially if low amounts are used and at lowconcentrations.

Novel salts of imidazoline derivatives of the formula I ##STR2## inwhich R represents hydrogen or alkyl,

Y represents nitro or cyano,

W represents an optionally substituted 5- or 6-membered heterocyclicradical and

Z represents one equivalent of an alkali metal or alkaline earth metalor of an [NR¹ R² R³ R⁴ ] grouping, wherein

R¹, R², R³ and R⁴ are identical or different and represent hydrogen,alkyl, optionally substituted cycloalkyl or optionally substitutedbenzyl, have been found.

It has furthermore been found that the salts of the imidazolinederivatives of the formula (I) are obtained by a process in whichimidazolines of the formula (II) ##STR3## in which R, Y and W have theabovementioned meaning, are reacted with hydroxides of the formula (III)

    Z--OH                                                      (III)

in which

Z has the abovementioned meaning, in the presence of a diluent.

Finally, it has been found that the novel salts of imidazolinederivatives of the formula (I) have highly pronounced biologicalproperties, and are suitable above all for controlling animal pests, inparticular insects, arachnids and nematodes, which occur in agriculture,in forestry, in the preservation of stored products and materials and inthe hygiene sector.

Formula (I) provides a general definition of the salts according to theinvention of imidazoline derivatives.

Preferred substituents and ranges of the radicals listed in the formulaementioned above and below are explained in the following.

R preferably represents hydrogen or C₁ -C₄ -alkyl.

Y preferably represents nitro or cyano.

W preferably represents a 5- or 6-membered heterocyclic radical whichcontains 1 or 2 identical or different heteroatoms, such as, preferably,nitrogen, oxygen or sulfur atoms, and is optionally substituted once tothree times in an identical or different manner, substituents which maybe mentioned being: halogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄-halogenoalkyl, C₁ -C₄ -halogenoalkoxy, C₁ -C₄ -alkylthio, C₁ -C₄-alkylsulfinyl, C₁ -C₄ -alkylsulfonyl, C₁ -C₄ -halogenoalkylthio, C₁ -C₄-halogenoalkylsulfinyl, C₁ -C₄ -halogenoalkylsulfonyl or C₁ -C₂-alkenyl.

Z preferably represents in each case one equivalent of lithium, sodium,potassium, rubidium, cesium, magnesium, calcium, ammonium, C₁ -C₄-alkylammonium, di-(C₁ -C₄ -alkyl)-ammonium, tri-(C₁ -C₄-alkyl)-ammonium, tetra-(C₁ -C₄ -alkyl)-ammonium, C₅ - or C₆-cycloalkyl-ammonium or di-(C₁ -C₂ -alkyl)-benzyl-anmmonium.

R particularly preferably represents hydrogen or methyl.

Y particularly preferably represents nitro or cyano.

W particularly preferably represents in each case optionally substitutedpyridyl, thiazolyl, oxazolyl, isothiazolyl or isoxazolyl, substituentswhich may be mentioned being: fluorine, chlorine, bromine, methyl,ethyl, trifluoromethyl, methoxy, trifluoromethoxy, methylthio,methylsulfinyl or methylsulfonyl.

Z particularly preferably in each case represents one equivalent oflithium, sodium, potassium, rubidium, cesium, magnesium, calcium,ammonium, methylammonium, dimethylammonium, trimethylammonium,tetramethylammonium, tetraethylammonium, tetra-n-propyl-ammonium,tetra-n-butylammonium or dimethyl-benzyl-ammonium.

Preferred compounds according to the invention are substances of theformulae (IA) to (ID): ##STR4## in which Z represents the abovementionedgeneral, preferred and particularly preferred meanings.

The radical definitions and explanations listed above, whether generalor in ranges of preference, apply correspondingly to the end productsand to the starting products and intermediates. These radicaldefinitions can be combined with one another as desired, thereforeincluding combinations between the respective ranges of preference.

Compounds of the formula (I) which are preferred according to theinvention are those in which a combination of the meanings listed aboveas preferred (preferably) is present.

Compounds of the formula (I) which are particularly preferred accordingto the invention are those in which a combination of the meanings listedabove as particularly preferred is present.

In the definitions of radicals listed above and below, hydrocarbonradicals, such as alkyl or alkenyl--including in combination withheteroatoms, such as alkoxy or alkylthio--are, where possible, in eachcase straight-chain or branched.

If, for example, 3H-1-(2-chloropyridin-5-yl)-2-nitroiminoimidazoline andlithium hydroxide are used as starting substances, the course of thereaction in the process according to the invention can be represented bythe following equation: ##STR5## The imidazolines of the formula (II) tobe used as starting substances in the process according to the inventionare known (cf., for example, EP-A 0 259 738 and EP-A 0 315 826), and/orthey can be prepared by known methods (cf., for example, theabovementioned literature references).

The hydroxides of the formula (III) furthermore to be used as startingsubstances in the process according to the invention are generally knowncompounds.

The process according to the invention is carried out in the presence ofa diluent. Diluents which can preferably be used are water andorganic/aqueous systems, it being possible for all the customarywater-miscible organic solvents to be employed. Examples which may bementioned are ketones, such as acetone, methyl ethyl ketone or methylisobutyl ketone; nitrites, such as acetonitrile or propionitrile, andalcohols, such as methanol or ethanol.

The reaction temperatures can be varied within a substantial range inthe process according to the invention. The reaction is in generalcarried out at temperatures between 0 and 100° C., preferably between 0and 60° C.

In carrying out the process according to the invention, in general 0.9to 1.5 mol, preferably 0.95 to 1.2 mol or molar equivalents of ahydroxide of the formula (III) are employed per mol of imidazoline ofthe formula (II).

Working up and isolation of the end products are carried out in thegenerally known manner.

In some cases, it proves advantageous to employ the compounds of theformula (III) in the form of their alcoholates.

The active compounds are suitable for controlling animal pests, inparticular insects, arachnids and nematodes, which are encountered inagriculture, in forestry, in the protection of stored products and ofmaterials, and in the hygiene field, and have good plant tolerance andfavourable toxicity to warm-blooded animals. They can preferably be usedas plant protection agents. They are active against normally sensitiveand resistant species and against all or some stages of development. Theabovementioned pests include:

From the order of the Isopoda, for example, Oniscus asellus,Armadillidium vulgare and Porcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus.

From the order of the Chilopoda, for example, Geophilus carpophagus andScutigera spec.

From the order of the Symphyla, for example, Scutigerella immaculata.

From the order of the Thysanura, for example, Lepisma saccharina.

From the order of the Collembola, for example, Onychiurus armatus.

From the order of the Orthoptera, for example, Blatta orientalis,Periplaneta americana, Leucophaea maderae, Blattella germanica, Achetadomesticus, Gryllotalpa spp., Locusta migratoria migratorioides,Melanoplus differentialis and Schistocerca gregaria.

From the order of the Dermaptera, for example, Forficula auricularia.

From the order of the Isoptera, for example, Reticulitermes spp.

From the order of the Anoplura, for example, Pediculus humanus corporis,Haematopinus spp. and Linognathus spp.

From the order of the Mallophaga, for example, Trichodectes spp. andDamalinea spp.

From the order of the Thysanoptera, for example, Hercinothrips femoralisand Thrips tabaci.

From the order of the Heteroptera, for example, Eurygaster spp.,Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodniusprolixus and Triatoma spp.

From the order of the Homoptera, for example, Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosomalanigerum, Hyalopterus arundinis, Phylloxera vastatrix, Pemphigus spp.,Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi,Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecaniumcorni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens,Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and Psyllaspp.

From the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletisblancardella, Hyponomeuta padella, Plutella maculipennis, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltiaspp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestrabrassicae, Panolis flammea, Spodoptera litura, Spodoptera spp.,Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyraustanubilalis, Ephestia kuehniella, Galleria mellonella, Tineolabisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoeciapodana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella,Homona magnanima and Tortrix viridana.

From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus,Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedoncochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachnavarivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp.,Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderrnaspp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus,Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp.,Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha,Amphimallon solstitialis and Costelytra zealandica.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis and Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleaeand Tipula paludosa.

From the order of the Siphonaptera, for example, Xenopsylla cheopis andCeratophyllus spp.

From the order of the Arachnida, for example, Scorpio maurus andLatrodectus mactans.

From the order of the Acarina, for example, Acarus siro, Argas spp.,Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptrutaoleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalommaspp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp.,Tarsonemus spp., Bryobia praetiosa, Panonychus spp. and Tetranychus spp.

The phytoparasitic nematodes include, for example, Pratylenchus spp.,Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans,Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp.,Longidorus spp., Xiphinema spp. and Trichodorus spp.

The compounds of the formula (I) according to the invention aredistinguished in particular by a high insecticidal activity.

They can be employed particularly successfully to control plant-damaginginsects, such as, for example, against the larvae of the mustard beetle(Phaedon cochlaeriae), the caterpillars of the cabbage moth (Plutellamaculipennis), the green rice cicada (Nephotettix cinctriceps), thecaterpillars of the owlet moth (Spodoptera frugiperda) or peach leafaphids (Mycus persicae).

The active compounds can be converted into the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,dusts, pastes, soluble powders, granules, suspension-emulsionconcentrates, natural and synthetic materials impregnated with activecompound, and very fine capsules in polymeric substances.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is liquid solvents and/orsolid carriers, optionally with the use of surface-active agents, thatis emulsifying agents and/or dispersing agents, and/or foam-formingagents.

In the case of the use of water as an extender, organic solvents can,for example, also be used as auxiliary solvents. As liquid solvents,there are suitable in the main: aromatics, such as xylene, toluene oralkylnaphthalenes, chlorinated aromatics or chlorinated aliphatichydrocarbons, such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, forexample mineral oil fractions, mineral and vegetable oils, alcohols,such as butanol or glycol as well as their ethers and esters, ketones,such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethyl sulfoxide, as well as water.

As solid carriers there are suitable: for example ammonium salts andground natural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly disperse silica, alumina and silicates; assolid carriers for granules there are suitable: for example crushed andfractionated natural rocks such as calcite, marble, pumice, sepioliteand dolomite, as well as synthetic granules of inorganic and organicmeals, and granules of organic material such as sawdust, coconut shells,maize cobs and tobacco stalks; as emulsifying and/or foam-forming agentsthere are suitable: for example non-ionic and anionic emulsifiers, suchas polyoxyethylene fatty acid esters, polyoxyethylene fatty alcoholethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates as well as albumen hydrolysis products; asdispersing agents there are suitable: for example lignin sulfite wasteliquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95% by weight ofactive compound, preferably between 0.5 and 90%.

The active compound according to the invention can be present in itscommercially available formulations and in the use forms, prepared fromthese formulations, as a mixture with other active compounds, such asinsecticides, attractants, sterilizing agents, bactericides, acaricides,nematicides, fumgicides, growth regulating substances or herbicides. Theinsecticides include, for example, phosphates, carbamates, carboxylates,chlorinated hydrocarbons, phenylureas, substances produced bymicroorganisms and the like.

Particularly suitable mixing partners are, for example, the following:

Fungicides:

2-aminobutane;2-anilino-4-methyl-6-cyclopropyl-pyrimidine;2',6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoro-methyl-1,3-thiazole-5-carboxanilide;2,6-dichloro-N-(4-trifluoromethylbenzvl)benzamide;(E)-2-methoxyimino-N-methyl-2-(2-phenoxyphenyl)-acetamide;8-hydroxyquinoline sulfate; methyl(E)-2-{2-[6-(2-cyanophenoxy)-pyrimidin-4-yloxy]-phenyl}-3-methoxyacrylate;methyl (E)-methoximino[alpha-(o-tolyloxy)-o-tolyl]acetate;2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol,blasticidin-S, bromuconazole, bupirimate, buthiobate,

calcium polysulfide, captafol, captan, carbendazim, carboxin,quinomethionate, chioroneb, chloropicrin, chlorothalonil, chlozolinate,cufraneb, cymoxanil, cyproconazole, cyprofuram,

dichlorophen, diclobutrazol, diclofluanid, diclomezin, dicloran,diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole,dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine,drazoxolon, edifenphos, epoxyconazole, ethirimol, etridiazole,

fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil,fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam,ferimzone, fluazinam, fludioxonil, fluoromide, fluquinconazole,flusilazole, flusulfamide, flutolanil, flutriafol, folpet,fosetyl-aluminum, fthalide, fuberidazole, furalaxyl, fuirmecyclox,guazatine,

hexachlorobenzene, hexaconazole, hymexazole,

imazalil, imibenconazole, iminoctadine, iprobenfos (IBP), iprodione,isoprothiolane, kasugamycin, copper formulations such as: copperhydroxide, copper naphthenate, copper oxychloride, copper sulfate,copper oxide, oxine-copper and Bordeaux mixture, mancopper, mancozeb,maneb, mepanipyrim, mepronil, metalaxyl, metconazole, methasulfocarb,methfuroxam, metiram, metsulfovax, myclobutanil, nickeldimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace,oxadixyl, oxamocarb, oxycarboxin, pefurazoate, penconazole, pencycuron,phosdiphen, phthalide, pimaricin, piperalin, polycarbamate, polyoxin,probenazole, prochloraz, procymidone, propamocarb, propiconazole,propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, quintozene(PCNB),

sulfur and sulfur formulations,

tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole,thicyofen, thiophanate-methyl, thiram, tolclophos-methyl, tolylfluanid,triadimefon, triadimenol, triazoxide, trichlamide, tricyclazole,tridemorph, triflumizole, triforine, triticonazole, validamycin A,vinclozolin, zineb, ziram.

Bacteincides:

bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,kasugamycin, octhilinone, furancarboxylic acid, oxytetracycline,probenazole, streptomycin, tecloftalam, copper sulfate and other copperformulations.

Insecticides/acanicides/nematicides

abamectin, AC 303 630, acephate, acrinathrin, alanycarb, aldicarb,alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A,azinphos M, azocyclotin, Bacillus thuringiensis, bendiocarb,benfuracarb, bensultap, betacyfluthrin, bifenthrin, BPMC, brofenprox,bromophos A, bufencarb, buprofezin, butocarboxin, butylpyridaben,cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap,CGA 157 419, CGA 184699, chloethocarb, chlorethoxyfos, chlorfenvinphos,chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M,cis-resmethrin, clocythrin, clofentezine, cyanophos, cycloprothrin,cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron,diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion,diflubenzuron, dimethoate, dimethylvinphos, dioxathion, disulfoton,

edifenphos, emamectin, esfen valerate, ethiofencarb, ethion,ethofenprox, ethoprophos, etrimphos,

fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion, fenobucarb,fenothiocarb, fenoxycarb, fenpropathrin, fenpyrad, fenpyroximate,fenthion, fenvalerate, fipronil, fluazinam, flucycloxuron,flucythrinate, flufenoxuron, flufenprox, fluvalinate, fonophos,formothion, fosthiazate, Iubfenprox, fiirathiocarb, HCH, heptenophos,hexaflumuron, hexythiazox, imidacloprid, iprobenfos, isazophos,isofenphos, isoprocarb, isoxathion, ivermectin, lambda-cyhalothrin,lufenuron, malathion, mecarbam, mevinphos, mesulfenphos, metaldehyde,methacrifos, methamidophos, methidathion, methiocarb, methomyl,metolcarb, milbemectin, monocrotophos, moxidectin,

naled, NC 184, NI 25, nitenpyram,

omethoate, oxamyl, oxydemethon M, oxydeprofos,

parathion A, parathion M, permethrin, phenthoate, phorate, phosalone,phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M, pirimiphos A,profenofos, promecarb, propaphos, propoxur, prothiofos, prothoate,pymetrozin, pyrachlophos, pyradaphenthion, pyresmethrin, pyrethrim,pyridaben, pyrimidifen, pyriproxifen, quinalphos,

RH 5992,

salithion, sebufos, silafluofen, sulfotep, sulprofos,

tebufenozide, tebufenpyrad, tebupirimphos, teflubenzuron, tefluthrin,temephos, terbam, terbufos, tetrachlorvinphos, thiafenox, thiodicarb,thiofanox, thiomethon, thionazin, thuringiensin, tralomethrin,triarathen, triazophos, triazuron, trichlorfon, triflumuron,trimethacarb,

vamidothion, XMC, xylylcarb, YI 5301/5302, zetamethrin.

A mixture with other known active compounds, such as herbicides, or withfertilizers and growth regulators, is also possible.

The active compounds according to the invention can fuirthermore bepresent in their commercially available formulations and in the useforms, prepared from these formulations, as a mixture with synergisticagents. Synergistic agents are compounds which increase the action ofthe active compounds, without it being necessary for the synergisticagent added to be active itself.

The active compound content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to95% by weight of active compound, preferably between 0.0001 and 1% byweight.

The compounds are employed in a customary manner appropriate for the useforms.

When used against hygiene pests and pests of stored products, the activecompound is distinguished by an outstanding residual action on wood andclay and by a good stability to alkali on limed substrates.

The active compounds according to the invention not only act againstplant pests, hygiene pests and pests of stored products, but also in theveterinary sector against animal parasites (ectoparasites), such as hardticks, soft ticks, mange mites, harvest mites, flies (biting andlicking), parasitic fly larvae, lice, hair lice, feather lice and fleas.These parasites include:

From the order of the Anoplurida, for example, Haematopinus spp.,Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp.

From the order of the Mallophagida and the suborders Amblycerina andIschnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Wemeckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp. and Felicola spp.

From the order of the Diptera and the suborders Nematocerina andBrachycerina, for example, Aedes spp., Anopheles spp., Culex spp.,Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp.,Culicoides spp., Chrysops spp., Hybromitra spp., Atylotus spp., Tabanusspp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp.,Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fanniaspp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp.,Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp.,Gasterophilus spp., Hippobosca spp., Lipoptena spp. and Melophagus spp.

From the order of the Siphonapterida, for example, Pulex spp.,Ctenocephalides spp., Xenopsylla spp. and Ceratophyllus spp.

From the order of the Heteropterida, for example, Cimex spp., Triatomaspp., Rhodnius spp. and Panstrongylus spp.

From the order of the Blattarida, for example, Blatta orientalis,Periplaneta americana, Blattela germanica and Supella spp.

From the subclass of the Acaria (Acarida) and the orders of the Meta-and Mesostigmata, for example, Argas spp., Ornithodorus spp., Otobiusspp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp.,Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp.,Raillietia spp., Pneumonyssus spp., Sternostoma spp. and Varroa spp.

From the order of the Actinedida (Prostigmata) and Acaridida(Astigmata), for example, Acarapis spp., Cheyletiella spp.,Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp.,Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.

The active compounds according to the invention of the formula (I) arealso suitable for combating arthropods which infest agriculturalproductive livestock such as, for example, cattle, sheep, goats, horses,pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geeseand bees, other pets, such as, for example, dogs, cats, cage birds andaquarium fish, and also so-called test animals, such as, for example,hamsters, guinea pigs, rats and mice. By combating these arthropodscases of death and reductions in productivity (for meat, milk, wool,hides, eggs, honey etc.) should be diminished, so that more economic andeasier animal husbandry is possible by use of the active compoundsaccording to the invention.

The active compounds according to the invention are used in theveterinary sector in a known manner by enteral administration in theform of, for example, tablets, capsules, potions, drenches, granules,pastes, boli, the feed-through process and suppositories, by parenteraladministration, such as, for example, by injections (intra-muscular,subcutaneous, intravenous, intraperitoneal etc.), implants, by nasaladministration, by dermal use in the form, for example, of dipping orbathing, spraying, pouring on and spotting on, washing and powdering,and also with the aid of moulded articles containing the activecompound, such as collars, ear tags, tail tags, limb bands, halters,marking devices, etc.

When used for livestock, poultry, pets and the like, the activecompounds of the formula (I) can be used as formulations (for examplepowders, emulsions, free-flowing mixtures), which comprise the activecompounds in an amount of 1 to 80% by weight, directly or after 100- to10,000-fold dilution, or they can be used as a chemical bath.

It has furthermore been found that the compounds of the formula (I)according to the invention have a potent insecticidal action againstinsects which destroy industrial materials.

The following insects may be mentioned as examples and as preferred--butwithout a limitation:

beetles, such as

Hylotrupes bajulus, Chlorophorus pilosis, anobium punctatum, Xestobiumrufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Emobius mollis,Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis,Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthesrugicollis; Xyleborus spec. Tryptodendron spec. Apate monachus,Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. andDinoderus minutus.

Hymenopterans, such as

Sirex juvencus, Urocerus gigas, Urocerus gigas taignus and Urocerusaugur.

Termites, such as

Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola,Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermeslucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis,Coptotermes formosanus.

Bristletails, such as Lepisma saccarina.

Industrial materials in the present connection are to be understood asmeaning non-living materials, such as, preferably, plastics, adhesives,sizes, papers and cards, leather, wood and processed wood products andpaints.

The material to be preserved against attack by insects is especiallypreferably wood and processed wood products.

Wood and processed wood products which are to be preserved by the agentaccording to the invention or mixtures comprising this are to beunderstood as meaning, for example: building timber, wooden beams,railway sleepers, bridge components, boat jetties, wooden vehicles,crates, pallets, containers, telegraph poles, wood paneling, woodenwindows and doors, plywood, chipboard, joinery or wooden products whichare used quite generally in housebuilding or in building joinery.

The active compounds can be used as such, in the form of concentrates orin generally customary formulations, such as powders, granules,solutions, suspensions, emulsions or pastes.

The formulations mentioned can be prepared in a manner known per se, forexample by mixing the active compounds with at least one solvent ordiluent, emulsifier, dispersing agent and/or binder or fixing agent, awater-repellent, if appropriate siccatives and UV stabilizers and ifappropriate dyestuffs and pigments, as well as other processingauxiliaries.

The insecticidal compositions or concentrates used for preservation ofwood and derived timber products comprise the active compound accordingto the invention in a concentration of 0.0001 to 95% by weight, inparticular 0.001 to 60% by weight.

The amount of the compositions or concentrates which are employeddepends on the nature and the occurrence of the insects and on themedium. The optimum amount employed can be determined for the use ineach case by a series of tests. In general, however, it is sufficient toemploy 0.0001 to 20% by weight, preferably 0.001 to 10% by weight, ofthe active compound, based on the material to be preserved.

The solvent and/or diluent used is an organic chemical solvent orsolvent mixture and/or an oily or oil-like organic chemical solvent orsolvent mixture of low volatility and/or a polar organic chemicalsolvent or solvent mixture and/or water and if appropriate an emulsifierand/or wetting agent.

Organic chemical solvents which are preferably employed are oily oroil-like solvents having an evaporation number above 35 and a flashpoint above 30° C., preferably above 45° C. Corresponding mineral oilsor aromatic fractions thereof or solvent mixtures containing mineraloil, preferably test benzine, petroleum and/or alkylbenzene, are used assuch water-insoluble, oily and oil-like solvents of low volatility.

Mineral oils having a boiling range from 170 to 220° C., test benzinehaving a boiling range from 170 to 220° C., spindle oil having a boilingrange from 250 to 350° C., petroleum or aromatics having a boiling rangefrom 160 to 280° C., terpentine oil and the like are advantageouslyemployed.

In a preferred embodiment, liquid aliphatic hydrocarbons having aboiling range from 180 to 210° C. or high-boiling mixtures of aromaticand aliphatic hydrocarbons having a boiling range from 180 to 220° C.and/or spindle oil and/or monochloronaphthalene, preferablyα-monochloronaphthalene, are used.

The organic oily or oil-like solvents of low volatility and having anevaporation number above 35 and a flash point above 30° C., preferablyabove 45° C., can be replaced in part by organic chemical solvents ofhigh or medium volatility, providing that the solvent mixture likewisehas an evaporation number above 35 and a flash point above 30° C.,preferably above 45° C., and that the insecticide/fungicide mixture issoluble or emulsifiable in this solvent mixture.

According to a preferred embodiment, some of the organic chemicalsolvent or solvent mixture or an aliphatic polar organic chemicalsolvent or solvent mixture is replaced. Aliphatic organic chemicalsolvents containing hydroxyl and/or ester and/or ether groups, such as,for example, glycol ethers, esters or the like, are preferably used.

Organic chemical binders which are used in the context of the presentinvention are the synthetic resins and/or binding drying oils which arewater-dilutable and/or soluble or dispersible or emulsifiable in theorganic chemical solvents employed and are known per se, in particularbinders consisting of or comprising an acrylate resin, a vinyl resin,for example polyvinyl acetate, polyester resin, polycondensation orpolyaddition resin, polyurethane resin, alkyd resin or modified alkydresin, phenolic resin, hydrocarbon resin, such as indene-cumarone resin,silicone resin, drying vegetable and/or drying oils and/or physicallydrying binders based on a natural and/or synthetic resin.

The synthetic resin used as binder can be employed in the form of anemulsion, dispersion or solution. Bitumen or bituminous substances canalso be used as binders in an amount of up to 10% by weight. Inaddition, dyestuffs, pigments, water-repellent agents, odor correctantsand inhibitors or anticorrosion agents and the like which are known perse can be employed.

According to the invention, the composition or concentrate preferablycomprises at least one alkyd resin or modified alkyd resin and/or onedrying vegetable oil as organic chemical binder. Alkyd resins having anoil content of more than 45% by weight, preferably 50 to 68% by weight,are preferably used according to the invention.

All or some of the binder mentioned can be replaced by a fixing agent(mixture) or a plasticizer (mixture). These additives are intended toprevent evaporation of the active compounds and crystallization orprecipitation. They preferably replace 0.01 to 30% of the binder (basedon 100% of the binder employed).

The plasticizers originate from the chemical classes of phthalic acidesters, such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoricacid esters, such as tributyl phosphate, adipic acid esters, such asdi-(2-ethylhexyl) adipate, stearates, such as butyl stearate or amylstearate, oleates, such as butyl oleate, glycerol ethers or highermolecular weight glycol ethers, glycerol esters and p-toluenesulfonicacid esters.

Fixing agents are based chemically on polyvinyl alkyl ethers, such as,for example, polyvinyl methyl ether, or ketones, such as benzophenone orethylenebenzophenone.

A possible solvent or diluent is, in particular, also water, ifappropriate mixed with one or more of the abovementioned organicchemical solvents or diluents, emulsifiers and dispersing agents.

Particularly effective wood preservation is achieved by impregnationprocesses on a large industrial scale, for example vacuum, double vacuumor pressure processes.

The ready-to-use compositions can also comprise other insecticides, ifappopriate, and also comprise one or more fungicides, if appropriate.

Possible additional mixing partners are, preferably, the insecticidesand fungicides mentioned in WO 94/29 268. The compounds mentioned inthis document are an explicit constituent of the present Application.

Especially preferred mixing partners can be insecticides, such aschlorpyriphos, phoxim, silafluofin, alphamethrin, cyfluthrin,cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25,flufenoxuron, hexaflumuron and triflumuron, and fungicides, such asepoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole,cyproconazole, metconazole, imazalil, dichlorfluanid, tolylfluanid,3-iodo-2-propinyl-butyl carbamate, N-octyl-isothiazolin-3-one and4,5-dichloro-N-octylisothiazolin-3-one.

The preparation and the use of the active compounds according to theinvention can be seen from the following examples.

PREPARATION EXAMPLES Example 1 ##STR6## 2.52 g (0.01 mol) of3H-1-(2-chloropyridin-5-yl)-2-nitroimino-imidazoline and 0.24 g (0.01mol) of lithium hydroxide are dissolved in 30 ml of water and thesolution is stirred at room temperature for a short time. The reactionsolution is filtered and the filtrate is concentrated in vacuo. Theresidue is dried in vacuo over phosphorus pentoxide.

2.43 g (93% of theory) of the lithium salt of3H-1-(2-chloropyridin-5-yl)-2-nitroimino-imidazoline are obtained.

MS spectrum (by the FAB method)*: MH⁺ =260.

[* FAB: fast atom bombardment]

The following compounds of the formula (I) are obtained analogously orin accordance with the general instructions for the preparation:

                                      TABLE 1                                     __________________________________________________________________________                                       (I)                                                                             #STR7##                                     -                                                                          Ex.                      MS Data                                                No. R Y W Z (FAB Method)                                                    __________________________________________________________________________      2 H NO.sub.2                                                                                           Na MH.sup.+  = 276                                    - 3 H NO.sub.2                                                                                        K MH.sup.+  = 292                                     - 4 H NO.sub.2                                                                                        Cs MH.sup.+  = 386                                    - 5 H NO.sub.2                                                                                        Rb MH.sup.+  = 338                                    - 6 H NO.sub.2                                                                                        N(CH.sub.3).sub.4 [M--N(CH.sub.3).sub.4                                     ].sup.⊖  = 252                                  - 7 H NO.sub.2                                                                                        Ca [M--Ca].sup.⊖  = 252                       - 8 H NO.sub.2                                                                                        N(C.sub.3 H.sub.7 -n).sub.4 [M--N(C.sub.3                                   H.sub.7 -n).sub.4 ].sup.⊖  = 252                                        - 9 H NO.sub.2                                                                N(C.sub.2 H.sub.5).sub.4 [M--N(C.sub.2                                      H.sub.5).sub.4 ].sup.⊖  = 252                   - 10 H NO.sub.2                                                                                       N(C.sub.4 H.sub.9 -n).sub.4 [M--N(C.sub.4                                   H.sub.9 -n).sub.4 ].sup.⊖  = 252             __________________________________________________________________________

USE EXAMPLES

The compound shown below is employed as the comparison substance in thefollowing use examples: ##STR17## Compound (A) known from EP-A 0 315 826

1-(2-Chloropyridin-5-yl)-3-methyl-2-nitroimino-imidazoline

Example A Phaedon larvae test

Solvent: 7 parts by weight of dimethylfornamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration. Cabbage leaves (Brassica oleracea) aretreated by being dipped into the preparation of the active compound ofthe desired concentration and are infested with mustard beetle larvae(Phaedon cochleariae), as long as the leaves are still moist. After thespecified period of time, the destruction in % is determined. 100% meansthat all the beetle larvae have been killed; 0% means that none of thebeetle larvae has been killed.

In this test, at an active compound concentration of, for example,0.01%, for example, the compound according to Preparation Example 1caused a destruction of 90% and the compounds of Preparation Examples 2,3, 4 and 5 caused a destruction of 100%, in each case after 7 days,while the known compound (A) showed a destruction of only 10%.

Example B Plutella test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration. Cabbage leaves (Brassica oleracea) aretreated by being dipped into the preparation of active compound of thedesired concentration and are infested with caterpillars of thediamond-back moth (Plutella maculipennis) while the leaves are stillmoist. After the specified period of time, the destruction in % isdetermined. 100% means that all the caterpillars have been killed; 0%means that none of the caterpillars has been killed.

In this test, at an active compound concentration of, for example, 0.1%,for example, the compounds according to Preparation Examples 2, 3, 4 and5 caused a destruction of 100% and the compound of Preparation Example 6caused a destruction of 85%, in each case after 7 days, while the knowncompound (A) showed a destruction of only 25%.

Example C Spodoptea frugiperda test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration. Cabbage leaves (Brassica oleracea) aretreated by being dipped into the preparation of active compound of thedesired concentration and are infested with caterpillars of the owletmoth (Spodoptera frugiperda), as long as the leaves are still moist.After the specified period of time, the destruction in % is determined.100% means that all the caterpillars have been killed; 0% means thatnone of the caterpillars has been killed.

In this test, for example, the compounds according to PreparationExamples 1, 2, 3, 4, 5 and 6 caused a destruction of 100% after 7 daysat an active compound concentration of, for example, 0.1%, while theknown compound (A) showed a destruction of only 50%.

Example D Nephotettix test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration. Rice seedlings (Oryza sativa) are treatedby being dipped into the preparation of active compound of the desiredconcentration and are infested with larvae of the green rice cicada(Nephotettix cincticepts), as long as the seedlings are still moist.After the specified period of time, the destruction in % is determined.100% means that all the cicadas have been killed; 0% means that none ofthe cicadas has been killed.

In this test, for example, the compounds according to PreparationExamples 1, 2, 3, 4, 5 and 6 caused a destruction of 100% after 6 daysat an active compound concentration of, for example, 0.001%, while theknown compound (A) showed a destruction of only 50%.

Example E Myzus penicae--sachet test

Solvent: Water, depending on the solubility, acetone

A 0.1% stock solution in the appropriate solvent was prepared for eachof the active compounds. The stock solution was diluted to theappropriate test concentration with a 15% strength solution of sucrosein water.

The particular active compound solution was pipetted into a syntheticdouble membrane (=sachet) of parafilm. The double membrane is drawn overa vessel which holds 15 adult peach aphids (Mycus persicae). In thistest method, the aphids take in the active compound exclusively orally.

After the specified period of time, the destruction in percent isdetermined at various concentrations. The LC 50 values are calculated bymeans of Probit analysis. The LC 50 value indicates the concentration atwhich 50% of the animals employed are killed. The lower the LC 50 value,the better the action of the preparation.

In this test, for example, LC 50 values of between 0.006 ppm and 0.048ppm result for the compounds of Preparation Examples 1, 2, 3, 4, 5 and 6after 2 days, while the known compound (A) has an LC 50 value of 0.15.

                  TABLE E                                                         ______________________________________                                        (plant-damaging insects)                                                        Myzus persicae-Sachettest                                                                                LC 50 value after                                  Active compound 2 d in ppm                                                  ______________________________________                                                                   0,15 8##                                              -                                                                                                     0,006 ##                                              -                                                                                                     0,017 ##                                              -                                                                                                     0,048 ##                                              -                                                                                                     0,023 ##                                              -                                                                                                     0,014 ##                                              -                                                                                                     0,0234##                                           ______________________________________                                    

We claim:
 1. A compound of the formula (I): ##STR25## in which Rrepresents hydrogen or alkyl,Y represents nitro or cyano, W representsan unsubstituted or substituted 5- or 6-membered heterocyclic radical,and Z represents one equivalent of an alkali metal or alkaline earthmetal other than sodium or of an [NR¹ R² R³ R⁴ ] grouping, whereinR¹,R², R³, and R⁴ are identical or different and represent hydrogen, alkyl,unsubstituted or substituted cycloalkyl or unsubstituted or substitutedbenzyl.
 2. Process for the preparation of a compound of the formula (I)according to claim 1, said process comprising reacting a compound of theformula (II): ##STR26## in which R represents hydrogen or alkyl,Yrepresents nitro or cyano, and W represents an unsubstituted orsubstituted 5- or 6-membered heterocyclic radical,with a hydroxide ofthe formula (III):

    Z--OH                                                      (III)

in which Z represents one equivalent of an alkali metal or alkalineearth metal other than sodium or of an [NR¹ R² R³ R⁴ ] grouping,whereinR¹, R², R³, and R⁴ are identical or different and representhydrogen, alkyl, unsubstituted or substituted cycloalkyl orunsubstituted or substituted benzyl; in the presence of a diluent.
 3. Apesticidal composition comprising a pesticidally effective amount of acompound according to claim 1 and a diluent.
 4. A method of controllingpests comprising applying to pests or their environment a pesticidallyeffective amount of a compound of the formula (I): ##STR27## in which Rrepresents hydrogen or alkyl,Y represents nitro or cyano, W representsan unsubstituted or substituted 5- or 6-membered heterocyclic radical,and Z represents one equivalent of an alkali metal or alkaline earthmetal other than sodium or of an [NR¹ R² R³ R⁴ ] grouping whereinR¹, R²,R³ and R⁴ are identical or different and represent hydrogen, alkyl,unsubstituted or substituted cycloalkyl or unsubstituted or substitutedbenzyl.